Method of making molybdenum-containing targets comprising three metal elements

ABSTRACT

The invention relates to sputter targets and methods for depositing a layer from a sputter target. The method preferably includes the steps of: placing a sputter target in a vacuum chamber; placing a substrate having a substrate surface in the vacuum chamber; reducing the pressure in the vacuum chamber to about 100 Torr or less; removing atoms from the surface of the sputter target while the sputter target is in the vacuum chamber (e.g., using a magnetic field and/or an electric field). The deposited layer preferably is a molybdenum containing alloy including about 50 atomic percent or more molybdenum, 0.5 to 45 atomic percent of a second metal element selected from the group consisting of niobium and vanadium; and 0.5 to 45 atomic percent of a third metal element selected from the group consisting of tantalum, chromium, vanadium, niobium, and titanium.

CLAIM OF PRIORITY

This application is a continuation of U.S. patent application Ser. No.12/827,550 filed Jun. 30, 2010, the contents of which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates generally to sputter targets, methods forpreparing sputter targets, methods of using the sputter targets inpreparing thin molybdenum containing films, such as those used to makeflat display panels (e.g., thin film transistor-liquid crystal displays)and photovoltaic cells, thin films made by the targets, and productsincorporating the same.

BACKGROUND

Sputter deposition is a technique used to produce a metallic layer invarious manufacturing processes used in the semiconductor and thephotoelectric industries. With advances in the semiconductor andphotoelectric industries, there are needs for sputter targets that meetone or more electrical requirements, durability requirements, andprocessability requirements. For example, there is a need for sputtertargets that that are easier to process, that are less expensive, andthat can be used to produce more uniform films. Furthermore, as the sizeof displays increases, the economic benefits of even modest improvementsin performance becomes amplified. Slight variations in compositions of asputter target could possibly lead to significant property changes.Moreover, different manners in which a target is made may lead to variedproperties resulting from a target made using the same composition.

Sputter targets made from a metal such as molybdenum, methods forpreparing them, and their use in flat panel displays are described inU.S. Pat. No. 7,336,336 B2, and in U.S. Patent Application PublicationNo. 2005/0189401A1 by Butzer et al, published on Sep. 1, 2005, each ofwhich is incorporated herein by reference in its entirety.

Sputter targets containing molybdenum and titanium, methods forpreparing them, and their use in flat panel displays are described inU.S. Pat. No. 7,336,824 B2 and in U.S. Patent Application PublicationNos. 2008/0314737A1 by Gaydos et al. published on Dec. 25, 2008,2007/0089984A1 by Gaydos et al., published on Apr. 26, 2007, and2007/0251820A1 by Nitta et al. published on Nov. 1, 2007, each of whichis incorporated herein by reference in its entirety.

Sputter targets containing molybdenum and a second metal are describedin U.S. Patent Application Publication No. 2004/0263055A1 by Chao at al.published on Dec. 30, 2004, 2007/0122649A1 by Lee et al. published onMay 31, 2007, and 2005/0230244A1 by Inoue et al. published on Oct. 20,2005, 2008/0073674A1 by Cho et al. published on Mar. 27, 2008, and2005/0191202A1 by Iwasaki et al. published on Sep. 1, 2005, each ofwhich is incorporated herein by reference in its entirety. In themanufacture of many devices, thin film products are often built up layerby layer with one or more material removal steps (e.g., etching) toremove one or more layers. To accommodate a wide selection of materialsfor enhancing design choice, it is attractive to be able to selectivelycontrol thin film etch rate (i.e., the rate of removal of material byetching). For example, it is attractive to be able to achieve certainetch rates by selection of an appropriate sputter target. It may bedesirable for a layer deposited from a sputter target to have an etchrate that is compatible with the etch rate of one or more other layers(e.g., etch rates that are the same or differ by less than about 25%)and/or to have an etch rate that is different (e.g., by about 25% ormore) from the etch rate of one or more other layers.

For example, for some applications there continues to exist a need forsputter targets that produce deposited layers having relatively highetch rates, such as etch rates in ferricyanide solution greater than theetch rate of a layer deposited from a sputter target consisting of 50atomic % molybdenum and 50 atomic % titanium. There is also a need forsputter targets for producing deposited layers having one or anycombination of a strong adhesion to substrates, a good barrierproperties, an ability to reduce or prevent the formation of coppersilicon compounds (such as copper silicide) when placed betweenSi-containing and Cu-containing layers, or a relatively low electricalresistivity (e.g., about 60 μΩ·cm or less). Additionally, there is aneed for sputter targets having one or more of the above properties,that is prepared from a heterogeneous material that can be processedinto a sputter target using a step of rolling.

SUMMARY OF THE INVENTION

One or more of the above needs may be surprisingly met with a sputtertarget including molybdenum (Mo), a second metal element selected fromthe group consisting of niobium (Nb) and vanadium (V) and a third metalelement selected from the group consisting of titanium, vanadium,niobium, chromium, and tantalum, wherein the third metal element isdifferent from the second metal element. The present invention in itsvarious teachings thus pertain to such compositions and sputter targetsmade with them, as well as resulting thin film products, and associatedmethods.

One aspect of the invention is a process for preparing a sputter targetand/or a blank that is used to manufacture a sputter target thatincludes a step of blending a first powder containing about 50 atomic %or more of molybdenum, a second powder containing about 50 atomic % ormore of a second metal element selected from the group consisting ofniobium and vanadium, and a third powder containing about 50 atomic % ormore of a third metal element selected from the group consisting oftitanium, vanadium, niobium, chromium, and tantalum, wherein the thirdmetal element is different from the second metal element.

Another aspect of the invention is directed at a sputter target and/or ablank that is used to manufacture a sputter target comprising: about 40atomic % or more molybdenum, based on the total number of atoms in thesputter target; about 1 atomic % or more of a second metal element,based on the total number of atoms in the sputter target wherein thesecond metal element is selected from the group consisting of niobiumand vanadium; and about 1 atomic % or more of a third metal element,based on the total number of atoms in the sputter target, wherein thethird metal element is selected from the group consisting of tantalum,chromium, vanadium, niobium, and titanium, and the third metal elementis different from the second metal element; so that the sputter targetmay be used for preparing a deposited film including an alloy, the alloycomprising molybdenum, the second metal element and the third metalelement.

Another aspect of the invention is directed at a sputter target and/or ablank that is used to manufacture a sputter target including at leastabout 40% by volume, based on the total volume of the sputter target, ofa first phase, wherein the first phase includes at least about 50 atomic% of a first metal element (and thus may be said to be rich in the firstmetal element), wherein the first metal element is molybdenum; fromabout 1 to about 40% by volume, based on the total volume of the sputtertarget, of a second phase, wherein the second phase includes at leastabout 50 atomic % of a second metal element (and thus may be said to berich in the second metal element), wherein the second metal element isniobium or vanadium, and from about 1 to about 40% by volume, based onthe total volume of the sputter target, of a third phase, wherein thethird phase includes at least about 50 atomic % of a third metal element(and thus may be said to be rich in the third metal element), whereinthe third metal element is selected from the group consisting oftitanium, vanadium, niobium, chromium, and tantalum, wherein the thirdmetal element is different from the second metal element, so that thesputter target may be used for preparing a deposited film including analloy, the alloy comprising molybdenum, the second metal element and thethird metal element. It will be appreciated that in the teachingsherein, the second metal element may be replaced by a combination ofvanadium and niobium. It will also be appreciated that in the teachingsherein, the third metal element may be replaced by a combination of twoor more metal elements selected from the group consisting of titanium,vanadium, niobium, chromium, and tantalum, with the proviso, that thecombination is different from the second metal element.

Another aspect of the invention is directed at a film (e.g., asputter-deposited film) including about 50 atomic % or more molybdenum,about 0.5 atomic % or more of a second metal element selected from thegroup consisting of niobium and vanadium, and about 0.5 atomic % or moreof a third element selected from the group consisting of titanium,vanadium, niobium, chromium, and tantalum, wherein the third metalelement is different from the second metal element. By way of example,one such film may have about 50 atomic % to about 90 atomic %molybdenum, about 5 atomic % to about 30 atomic % of the second metalelement (e.g., niobium or vanadium), and about 5 atomic % to about 30atomic % of the third metal element. The film may exhibit a relativelyhigh etch rate in accordance with the etch rate teachings herein.

Another aspect of the invention is directed at a multilayer structureincluding a film deposited from a sputter target described herein.

Another aspect of the invention is directed at a process for depositinga film on a substrate using a sputter target described herein.

The sputter targets of the present invention may advantageously be usedto deposit a film having generally high etch rates. For example, theetch rate of the deposited film in ferricyanide solution at 25° C. maybe about 100 nm/min or more, preferably about 150 nm/min or more, morepreferably about 200 nm/min or more, even more preferably about 225nm/min or more, even more preferably about 300 nm/min or more, and mostpreferably about 400 nm/min or more. The sputter target may be used todeposit a film having the following characteristics: a strong adhesionto substrates; good barrier properties; that substantially avoids theformation of copper silicide when placed between a silicon-containinglayer and a copper-containing layer; low electrical resistivity; or anycombination thereof. Advantageously, the sputter target may be formed ofa material capable of being deformed, such as by one or morethermomechanical deformation operations. For example the sputter targetmay be prepared from a material capable of being rolled (e.g., throughone or more rolling operations), preferably without cracking, so thatlarge sputter targets can be produced efficiently. It is also possibleto make large targets by joining multiple individually preformedstructures (e.g., blocks), e.g., by diffusion bonding via a hotisostatic processing operation, with or without powder between adjoiningpreformed structures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using secondaryelectron imaging. The sputter target preferably includes a molybdenumrich phase that includes 50 atomic % or more molybdenum, a niobium richphase that includes 50 atomic % or more niobium, and a tantalum richphase that includes 50 atomic % or more tantalum.

FIG. 2 is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium and tantalum using backscatteredelectron imaging. The sputter target preferably includes a molybdenumrich phase, a tantalum rich phase, and a niobium rich phase.

FIG. 3A is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using backscatteredelectron imaging. As illustrated in FIG. 3A, the sputter targetpreferably includes a molybdenum rich phase.

FIG. 3B is an illustrative energy dispersive x-ray spectroscopy graphshowing the frequency distribution of x-rays having energy from 0 to 20keV energy for a region of the sputter target of FIG. 3A. As illustratedin FIG. 3B, the sputter target may include a phase that is essentiallyentirely (e.g., about 90 atomic % or more, preferably about 95 atomic %or more, and more preferably about 98 atomic % or more) molybdenum.

FIG. 4A is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using backscatteredelectron imaging. As illustrated in FIG. 4A, the sputter targetpreferably includes a niobium rich phase.

FIG. 4B is an illustrative energy dispersive x-ray spectroscopy graphshowing the frequency distribution of x-rays having energy from 0 to 20keV energy for a region of the sputter target of FIG. 4A. FIG. 4Billustrates that the sputter target may have a phase that is essentiallyentirely (e.g., about 90 atomic % or more, preferably about 95 atomic %or more, and more preferably about 98 atomic % or more) niobium.

FIG. 5A is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using backscatteredelectron imaging. As illustrated in FIG. 5A, the sputter targetpreferably includes a tantalum rich phase.

FIG. 5B is an illustrative energy dispersive x-ray spectroscopy graphshowing the frequency distribution of x-rays having energy from 0 to 20keV energy for a region of the sputter target of FIG. 5A. FIG. 5Billustrates that the sputter target may have a phase that is essentiallyentirely (e.g., about 90 atomic % or more, preferably about 95 atomic %or more, and more preferably about 98 atomic % or more) tantalum.

FIG. 6A is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using backscatteredelectron imaging. As illustrated in FIG. 6A, the sputter target mayoptionally includes a phase that consists essentially of or evenentirely of an alloy of niobium and molybdenum. e.g., one that includesabout 10 atomic % or more niobium and about 10 atomic % or moremolybdenum. For example, the total concentration of niobium andmolybdenum in the alloy may be about 80 atomic % or more, preferablyabout 90 atomic % or more, preferably about 95 atomic % or more, andmore preferably about 98 atomic % or more.

FIG. 6B is an illustrative energy dispersive x-ray spectroscopy graphshowing the frequency distribution of x-rays having energy from 0 to 4keV energy for a region of the sputter target of FIG. 6A. FIG. 6Billustrates that the sputter target may have a phase that includesmolybdenum and niobium.

FIG. 7A is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using backscatteredelectron imaging. As illustrated in FIG. 7A, the sputter target mayoptionally includes a phase that consists essentially of or evenentirely of an alloy of tantalum and molybdenum, e.g., one that includesabout 10 atomic % or more tantalum and about 10 atomic % or moremolybdenum. For example, the total concentration of tantalum andmolybdenum in the alloy may be about 80 atomic % or more, preferablyabout 90 atomic % or more, more preferably about 95 atomic % or more,and most preferably about 98 atomic % or more.

FIG. 7B is an illustrative energy dispersive x-ray spectroscopy graphshowing the frequency distribution of x-rays having energy from 0 to 20keV energy for a region of the sputter target of FIG. 7A. FIG. 7Billustrates that the sputter target may have a phase that includesmolybdenum and tantalum.

FIGS. 8A and 8B are illustrative scanning electron micrographs of asurface of sputtered films deposited on a substrate using secondaryelectron imaging. The films are sputtered from a sputter targetincluding a molybdenum rich phase, a niobium rich phase, and a tantalumrich phase. The deposited film preferably include an alloy phasecontaining molybdenum, niobium and tantalum.

FIG. 9 is an illustrative scanning electron micrograph of across-section of a sputtered film deposited on a substrate. The film issputtered from a sputter target including a molybdenum rich phase, aniobium rich phase, and a tantalum rich phase. The deposited filmpreferably includes an alloy phase containing molybdenum, niobium andtantalum. The deposited film may have a columnar morphology, such as themorphology illustrated in FIG. 9.

FIGS. 10A, 10B and 10C are illustrative Auger Spectra of a multilayeredstructure including a silicon substrate, a first sputtered layerincluding molybdenum, niobium and tantalum, and a second sputtered layerof copper. The spectra illustrate the compositions of Cu, Si, Ta, Nb,and Mo versus depth, before (FIG. 10A) and after (FIG. 10B) annealingfor about 30 minutes at about 350° C. FIG. 10C is an illustrativeoverlay of the concentrations profiles before and after annealing in theregion of the interfaces between the layers.

FIG. 11 is an illustrative multi-layered structure including a substratelayer, a molybdenum containing layer, and a conductive layer. Themolybdenum containing layer preferably is deposited from a sputtertarget including a molybdenum rich phase, a niobium rich phase and atantalum rich phase.

DETAILED DESCRIPTION

The present invention, in its various aspects, makes use of a uniquecombination of materials to derive an attractive sputter target for usein the manufacture of one or more various devices (e.g., flat paneldisplays) that include a thin film layer, such as a thin film barrierlayer, tie layer, or otherwise. The deposited layers prepared from thesputter targets of the present invention have a surprising combinationof relatively low electrical resistivity, good adhesion to substratesand/or excellent barrier properties. As taught herein, the sputtertarget may be tailored to provide a relatively high etch rate (e.g., inferricyanide solution).

The sputter targets of the present invention employ three or moredifferent elements to achieve the desired performance properties.Without limitation, suitable sputter targets include material includingor consisting essentially of three metal elements, four metal elements,or five or more metal elements. For example, the sputter target mayinclude or consist substantially of molybdenum (i.e. Mo) and two or moreadditional elements (such as two, three or more elements) selected fromthe group consisting of titanium (i.e., Ti), vanadium (i.e., V),chromium (i.e., Cr), tantalum (i.e., Ta), and niobium (i.e., Nb),wherein at least one of the additional elements is niobium or vanadium.Preferred sputter targets include Mo, Ti, V, Cr, Ta, and Nb, present ata total concentration of about 60 atomic % or more, more preferablyabout 80 atomic % or more, even more preferably about 95 atomic % ormore, even more preferably about 99 atomic % or more, and mostpreferably about 99.5 atomic % or more, based on the total number ofatoms in the sputter target. Without limitation, deposited layersprepared from the sputter targets of the present invention may includeternary materials and/or quaternary materials.

The sputter targets may be used to produce (e.g., to deposit) a filmhaving at least one molybdenum containing layer (e.g., a barrier layer)that comprises molybdenum (e.g., at a concentration of at least 50atomic % based on the total number of atoms in the molybdenum containinglayer), a second metal element, and a third metal element. The depositedlayer may contain fewer phases than the sputter target. Withoutlimitation, exemplary deposited layers produced from the sputter targetmay contain one or two phases, whereas the sputter target from whichthey are prepared, preferably contain at least three phases (e.g., oneor more pure metal phases and/or one or more alloy phases). Morepreferably, the deposited layer includes or consists essentially of analloy phase, wherein the alloy includes molybdenum, the second metalelement and the third metal element. Even more preferably, the depositedlayer includes or consist substantially of an alloy phase, wherein thealloy includes molybdenum, the niobium and the third metal element. Mostpreferably, the deposited layer includes or consist substantially of analloy phase, wherein the alloy includes molybdenum, the niobium andtantalum.

Morphology of the Sputter Target

The sputter target may be a heterogeneous material including a pluralityof phases. The sputter target preferably comprises at least threephases. For example, the target may include, including one or more firstphases each comprising about 50 atomic % or more molybdenum, one or moresecond phases each comprising about 50 atomic % or more of a secondmetal element different from molybdenum, and one or more third phaseseach comprising at about 50 atomic % or more of a third metal elementdifferent from molybdenum and second metal elements. The second metalelement preferably is selected from the group consisting of niobium andvanadium. Most preferably, the second metal element is niobium. Thethird metal element is preferably selected from the group consisting oftitanium, chromium, vanadium, niobium, and tantalum. Most preferably,the third metal element is tantalum.

A second phase may differ from a first phase in one or any combinationof the following: the concentration of one, two or more elements,density, electrical resistivity, the bravais lattice structure, thesymmetry group, one or more lattice dimensions, or the crystallographicspace group. By way of example, a first phase and a second phase maydiffer in the concentration of one element by about 0.5 wt. % or more,by about 1 wt. % or more, by about 5 wt. % or more, or by about 20 wt. %or more. A third phase may differ from a first phase and/or a secondphase in one or any combination of the following: the concentration ofone, two or more elements, density, electrical resistivity, the bravaislattice structure, the symmetry group, one or more lattice dimensions,or the crystallographic space group. By way of example, theconcentration of an element in a third phase my differ from theconcentration of the element in a first phase, in a second phase, orboth, by about 0.5 wt. % or more, by about 1 wt. % or more, by about 5wt. % or more, or by about 20 wt. % or more. The sputter target mayinclude two phases (such as a first phase and a second phase or a thirdphase), wherein the difference between the densities of the two phasesis about 0.1 g/cm³ or more, preferably about 0.3 g/cm³ or more, morepreferably about 0.6 g/cm³, and most preferably about 1.2 g/cm³ or more.

The first phase, the second phase, and the third phase, may eachindependently include crystals characterized by one or more of the 14bravais lattice types. The bravais lattice of a phase may be triclinic,monoclinic (e.g., simple monoclinic or centered monoclinic),orthorhombic (e.g., simple base centered orthorhombic, body centeredorthorhombic, or face-centered orthorhombic), tetragonal (e.g., simpletetragonal or body-centered tetragonal), rhombohedral, hexagonal, orcubic (e.g., simple cubic, body-centered cubic or face-centered cubic).By way of example, the first phase, the second phase, and the thirdphase may each independently include or consist essentially of crystalshaving bravais lattices that are hexagonal, simple cubic, body-centeredcubic, and face-centered cubic, or any combination thereof. The one ormore second phases may include crystals having a bravais lattice that isthe same or different from the bravais lattice of the one or more firstphases. By way of example, the first phase may include a phase having abody-centered cubic bravais lattice, and the second phase may include aphase having a body-centered cubic bravais lattice, a hexagonal bravaislattice, or both. The one or more third phases may include crystalshaving a bravais lattice that is the same as or different from the oneor more first phases, that is different from the one or more secondphases, or any combination thereof. By way of example, the one or morethird phases may include or consist essentially of crystals having abody-centered cubic bravais lattice, a hexagonal bravais lattice, orboth.

It will be appreciated that the first phase of the sputter target mayinclude one or more first phases each including about 50 atomic % ormore molybdenum. By way of example, the first phase may include a phaseof substantially pure molybdenum, an alloy phase including molybdenumand a minor amount (i.e. less than 50 atomic %) of the second metalelement, an alloy phase including molybdenum and a minor amount of thethird metal element, or any combination thereof. The second phase of thesputter target may include on or more phases each including about 50atomic % or more of the second metal element. By way of example, thesecond phase may include a phase of substantially pure second metalelement, an alloy phase including the second metal element and a minoramount of molybdenum, an alloy phase including the second metal elementand a minor amount of the third metal element, or any combinationthereof. The third phase of the sputter target may include on or morephases each including about 50 atomic % or more of the third metalelement. By way of example, the third phase may include a phase ofsubstantially pure third metal element, an alloy phase including thethird metal element and a minor amount of molybdenum, an alloy phaseincluding the third metal element and a minor amount of the second metalelement, or any combination thereof.

The first phase, second phase, and third phase may each independently bediscrete phases, or continuous phases. Preferably the first phase is acontinuous phase. Without being bound by theory, it is believed that afirst phase that is continuous may improve the capability of rolling asputter target in order to increase its length, increase its width, orboth. Preferably the second phase is a discrete phase. Preferably thethird phase is a discrete phase. It will be appreciated that continuousphase refers to a phase that is co-continuous (i.e., there are aplurality of continuous phases) or to a continuous phase that is thesole continuous phase.

FIG. 1 is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium, and tantalum using secondaryelectron imaging. According to the teachings herein, other metalelements may be employed in the sputter target. With reference to FIG.1, the sputter target 10 may include a first phase 16, a second phase14, and a third phase 12. The first phase 16 of the sputter target 10may be a continuous phase, include 50 atomic % or more molybdenum (e.g.,about 75 atomic % or more molybdenum) or both. As illustrated in FIG. 1,the second phase 14, the third phase 12, or both, may be a discretephase (such as a discrete phase dispersed in the first phase). A secondphase, a third phase, or both that is a continuous phase (e.g., aco-continuous phase) is also within the scope of the invention. Thesecond phase 14 may include about 50 atomic % or more of a secondelement, such as niobium or vanadium, based on the total number of atomsin the second phase. The third phase 12 may include about 50 atomic % ormore of a third element, such as titanium, chromium, niobium, vanadiumor tantalum, based on the total number of atoms in the third phase. Asillustrated in FIG. 1, the volume of the one or more first phases may beabout 40 volume % or more, or about 50 volume % or more, based on thetotal volume of the sputter target. The volume of the one or more secondphases, the volume or the one or more third phases, and the total volumeof the one or more first and second phases, may be about 1 volume % ormore, or about 5 volume % or more, based on the total volume of thesputter target. The volume of the one or more second phases, the volumeor the one or more third phases, and the total volume of the one or morefirst phases and second phases, may each be about 50 volume % or less,or about 25 volume % or less, based on the total volume of the sputtertarget. The second phase, the third phase, or both may be generallyrandomly oriented. The second phase, the third phase, or both may begenerally elongated. Preferably the second phase, the third phase, orboth, have a length to width ratio of about 20:1 or less, about 10:1 orless, or about 5:1 or less. The second phase may include particleshaving an average length of about 0.3 μm or more, having an averagelength of about 200 μm or less, or both. The third phase may includeparticles having an average length of about 0.3 μm or more, having anaverage length of about 200 μm or less, or both. The length and/orvolume of a phase may be measured using scanning electron microscopy.Scanning electron microscopy may be supplemented by additional methods,such as energy dispersive x-ray spectroscopy, for measuring thecomposition of a phase.

FIG. 2 is an illustrative scanning electron micrograph of a sputtertarget including molybdenum, niobium and tantalum using backscatteredelectron imaging. According to the teachings herein, other metalelements may be employed in the sputter target. With reference to FIG.2, the sputter target 10 may include a first phase 16, a second phase14, and a third phase 12. Each of the individual phases may be asubstantially pure metallic phase (e.g., a phase that includes a metalin an amount of about 80 atomic % or more, about 90 atomic % or more, orabout 95 atomic % or more). The sputter target may also include an alloyphase, such as an alloy phase including molybdenum and tantalum 18,and/or an intermetallic phase.

The one or more first phases may optionally include both a relativelypure first phase and a highly alloyed first phase containing themolybdenum at a lower concentration than the relatively pure firstphase. For example, the relatively pure first phase may containmolybdenum at a concentration of about 80 atomic % or more, morepreferably about 90 atomic %, or more, based on the total number ofatoms in the relatively pure first phase. By way of example, theconcentration of molybdenum in the highly alloyed first phase may beabout 90 atomic % or less, about 80 atomic % or less, or about 70 atomic% or less. Preferably, the one or more first phases includes asufficient volume of material having a generally high molybdenumconcentration (e.g., about 60 atomic % or more molybdenum, about 70atomic % or more molybdenum, about 80 atomic % or more molybdenum, orabout 90 atomic % or more molybdenum) so that the sputter target can berolled in a step that increases the width, the length, or both, of thesputter target.

The one or more second phases may optionally include both a relativelypure second phase (e.g., a phase containing about 80 atomic % or more,more preferably about 90 or more atomic % of the second metal elementbased on the total number of atoms in the relatively pure second phase)and a highly alloyed second phase containing the second metal element ata lower concentration (e.g., at a concentration about 90 atomic % orless, or about 80 atomic % or less) than the relatively pure secondphase. The one or more third phases may optionally include both arelatively pure third phase (e.g., a phase containing about 80 atomic %or more, more preferably about 90 atomic % or more of the third metalelement based on the total number of atoms in the relatively pure thirdphase) and a highly alloyed third phase containing the third metalelement at a lower concentration (e.g., at a concentration about 90atomic % or less, or about 80 atomic % or less) than in the relativelypure third phase.

The volume of the one or more first phases preferably is sufficientlyhigh so that the first phase is a continuous phase (e.g., a matrix phasein which one or more other phases is dispersed). The volume of the oneor more first phases may be about 40% or more by volume, about 50% ormore by volume, about 60% or more by volume, or about 70% or more byvolume, based on the total volume of the sputter target. Preferably thevolume of the one or more first phases is greater than the volume of theone or more second phase. Preferably the volume of the one or more firstphases is greater than the volume of the one or more second phases. Thevolume of the one or more first phases may be about 99% or less byvolume, about 95% or less by volume, about 92% or less by volume, orabout 90% or less by volume, based on the total volume of the sputtertarget.

The volume of the one or more second phases, the one or more thirdphases, or the combination of the one or more second phases and the oneor more third phases may be about 1% or more by volume, about 2% or moreby volume, about 3% or more by volume, or about 5% or more by volume,based on the total volume of the sputter target. The volume of the oneor more second phases, the one or more third phases, or the combinationof the one or more second phases and the one or more third phases may beabout 50% or less by volume, about 45% or less by volume, about 40% orless by volume, about 35% or less by volume, about 30% or less byvolume, about 25% or less by volume, or about 20% or less by volume,based on the total volume of the sputter target.

The one or more first phases, the one or more second phases, and the oneor more third phases of the sputter target may each individually bediscrete phases, continuous phases, or co-continuous phases. Forexample, the sputter target may include a first phase that is acontinuous phase. Preferably, the one or more second phases includes adiscrete phases. For example a discrete second phase may be a discretephase within a first phase, or a discrete phase within the third phase.More, preferably, the sputter target includes a second phase including50 atomic % or more niobium or vanadium that is a discrete phase withina first phase including 50 atomic % or more molybdenum. Preferably, theone or more third phases includes a discrete phase. For example adiscrete third phase my be a discrete phase within the first phase, or adiscrete phase within the second phase. More preferably, the sputtertarget includes a third phase including 50 atomic % or more of titanium,chromium, niobium, vanadium, or tantalum that is a discrete phase withina first phase including 50 atomic % or more molybdenum. If the sputtertarget has at least two second phases, it may have a morphology in whichone of the second phases contains about 80 atomic % or more of thesecond metal element and is encapsulated by another of the second phasesthat contains a lower concentration of the second metal element. If thesputter target has at least two third phases, it may have a morphologyin which one of the third phases contains about 80 atomic % or more ofthe third metal element and is encapsulated by another of the thirdphases that contains a lower concentration of the third metal element.

The size of the domains (i.e., a contiguous region that may include oneor more grains of a phase) of one or more, or even all of the phases ofthe sputter target may be relatively large. For example, the size of thedomains of the one or more, or even all of the phases of the sputtertarget may be larger (e.g. by 50% or more, by about 100% or more, byabout 200% or more, by about 500% or more, or by about 1000% or more)than the size of the domains of the phase or phases of a deposited layerprepared from the sputter target. Without limitation the domain size(e.g., the number average length of the domains) of the one or morefirst phases, the one or more second phases, and/or the one or morethird phases, may be about 0.3 μm or more, preferably about 0.5 μm ormore, more preferably about 1 μm or more, and most preferably greater 3μm or more. In determining the domain sizes of the phases of the sputtertarget, all of the first phases may be considered as one phase, all ofthe second phases may be considered as one phase, and all of the thirdphases may be considered as one phase. Without limitation the domainsize (e.g., the number average length of the domains) of the one or morefirst phases, of the one or more second phases, and/or the one or morethird phases, may be about 200 μm or less, preferably about 100 μm orless, and more preferably about 50 μm or less. It will be appreciatedthat larger domain sizes may be employed in the sputter target. Forexample, as taught herein, one or more of the phases may be a continuousphase. The shape of the domains of the second phase, the third phase, orboth may be generally elongated. Preferably the second phase, the thirdphase, or both, have a length to width ratio of about 20:1 or less,about 10:1 or less, or about 5:1 or less.

FIG. 3A is a scanning electron micrograph (backscattered electrons) of aregion of a sputter target including molybdenum, niobium and tantalumincluding a molybdenum phase 16 and a point 32 in the molybdenum phase.FIG. 3B is an illustrative energy dispersive x-ray spectrograph taken atthe point 32 of FIG. 3A. The spectrograph of FIG. 3B includes only apeak 34 corresponding to molybdenum. As illustrated by FIG. 3B, thesputter target may include a region that includes a phase ofsubstantially pure molybdenum (i.e., including about 80 atomic % or moremolybdenum, about 90 atomic % or more molybdenum, or about 95 atomic %or more molybdenum).

FIG. 4A is a scanning electron micrograph (backscattered electrons) of aregion of a sputter target including molybdenum, niobium and tantalumincluding a niobium phase 14 and a point 42 in the niobium phase. FIG.4B is an illustrative energy dispersive x-ray spectrograph taken at thepoint 42 of FIG. 4A. The spectrograph of FIG. 4B includes only a peak 44corresponding to niobium. As illustrated by FIG. 4B, the sputter targetmay include a region that includes a phase of substantially pure secondmetal element (i.e., including about 80 atomic % or more of the secondmetal element, about 90 atomic % or more of the second metal element, orabout 95 atomic % or more of the second metal element), such as a phaseof substantially pure niobium, or a phase of substantially purevanadium.

FIG. 5A is a scanning electron micrograph (backscattered electrons) of aregion of a sputter target including molybdenum, niobium and tantalumincluding a tantalum phase 12, a molybdenum phase 16, and a point 52 inthe tantalum phase. FIG. 5B is an illustrative energy dispersive x-rayspectrograph taken at the point 52 of FIG. 5A. The spectrograph of FIG.5B includes only peaks 54, 54′, 54″, and 54′″ corresponding to tantalum.As illustrated by FIG. 5B, the sputter target may include a region thatincludes a phase of substantially pure third metal element (i.e.,including about 80 atomic % or more of the third metal element, about 90atomic % or more of the third metal element, or about 95 atomic % ormore of the third metal element), such as a phase of substantially puretantalum, a phase of substantially pure titanium, or a phase ofsubstantially pure chromium.

FIG. 6A is a scanning electron micrograph (backscattered electrons) of aregion of a sputter target including molybdenum, niobium and tantalum.The micrograph illustrates that the sputter target includes a niobiumphase 14, a molybdenum phase 16, a molybdenum/niobium alloy phase 17,and a point 62 in the alloy phase 17. FIG. 6B is an illustrative energydispersive x-ray spectrograph taken at the point 62 of FIG. 6A. Thespectrograph of FIG. 6B includes both peaks 64 corresponding to Mo and66 corresponding to Nb. As illustrated by FIG. 6B, the sputter targetmay include a region that includes an alloy phase including the secondmetal element and molybdenum, such as an alloy of niobium andmolybdenum.

FIG. 7A is a scanning electron micrograph (backscattered electrons) of aregion of a sputter target including molybdenum, niobium and tantalum.The micrograph illustrates that the sputter target includes a tantalumphase 12, a molybdenum phase 16, a molybdenum/tantalum alloy phase 19,and a point 72 in the alloy phase 19. FIG. 7B is an illustrative energydispersive x-ray spectrograph taken at the point 72 of FIG. 7A. Thespectrograph of FIG. 7B includes both peaks 74 corresponding to Mo and76, 76′ corresponding to tantalum. As illustrated by FIG. 7B, thesputter target may include a region that includes an alloy phaseincluding the third metal element and molybdenum, such as an alloy oftantalum and molybdenum.

Molybdenum Concentration of the Sputter Target

The total concentration of molybdenum in the target may be about 50atomic % or more, preferably about 55 atomic % or more, more preferablyabout 60 atomic % or more, even more preferably about 63 atomic % ormore, and most preferably about 65 atomic % or more. The concentrationof molybdenum in the target may be about 95 atomic % or less, preferablyabout 90 atomic % or less, more preferably about 85 atomic % or less,even more preferably about 83 atomic % or less, and most preferablyabout 81 atomic % or less.

Additional Elements:

In addition to the molybdenum, the target includes at least twoadditional metal elements (i.e., a second metal element and a thirdmetal element). The second metal element and the third metal element mayeach independently have an atomic mass greater than or less than theatomic mass of molybdenum. For example, the second metal element mayhave an atomic mass than it less than the atomic mass of molybdenum andthe third metal element may have an atomic mass that is greater than theatomic mass of molybdenum. As another example, the second metal elementand the third metal element may both have an atomic mass less than theatomic mass of molybdenum. The second and third metal elements may beselected from IUPAC group 4, 5, and 6 elements. Preferably the targetincludes two or more elements (i.e., the second metal element and thethird metal element) selected from the group consisting of titanium,tantalum, niobium, chromium, vanadium, hafnium, zirconium, and tungsten.More preferably the target includes two or more elements selected fromthe group consisting of titanium, tantalum, niobium, chromium, andvanadium. As such, the second metal element of the sputter target may bean element selected from the group consisting of titanium, tantalum,niobium, chromium, and vanadium. Similarly, the third metal element ofthe sputter target may be an element different from the second metalelement and selected from the group consisting of titanium, tantalum,niobium, chromium, and vanadium. More preferred second metal elementsinclude niobium and vanadium. Most preferably the second metal elementsis niobium. More preferred third metal elements include an elementselected from the group consisting of titanium, chromium, niobium,vanadium, and tantalum, with the proviso that the third metal element isdifferent from the second metal element. Most preferably, the thirdmetal element is tantalum.

Without limitation, exemplary targets include targets including,consisting essentially of, or consisting of: molybdenum, niobium, andtantalum; molybdenum, niobium and chromium; molybdenum, niobium, andvanadium; molybdenum, niobium, and titanium; molybdenum, vanadium, andtantalum; molybdenum, vanadium, and chromium; molybdenum, vanadium, andtitanium; molybdenum, niobium, vanadium, and chromium; molybdenum,niobium, vanadium, and tantalum; molybdenum, niobium, vanadium, andtitanium; or molybdenum, niobium, vanadium, titanium and tantalum.Preferred targets include targets including, consisting essentially of,or consisting of: molybdenum, niobium, and tantalum; molybdenum, niobiumand chromium; molybdenum, niobium, and vanadium; molybdenum, niobium,and titanium; molybdenum, vanadium, and tantalum; molybdenum, vanadium,and chromium; or molybdenum, vanadium, and titanium. Most preferredtargets include targets including, consisting essentially of, orconsisting of molybdenum, niobium, and tantalum.

The concentration of the second metal element, the third metal element,or the combination of the second and third metal element in the sputtertarget may be about 0.1 atomic % or more, preferably about 0.5 atomic %or more, more preferably about 1 atomic % or more, even more preferablyabout 2 atomic % or more, and most preferably about 5 atomic % or more,based on the total concentration of atoms in the target. Theconcentration of the second metal element, the third metal element, orthe combination of the second and third metal element in the sputtertarget may be less than about 50 atomic %, preferably about 45 atomic %or less, more preferably about 40 atomic % or less, even more preferablyabout 35 atomic % or less and most preferably about 30 atomic % or less,based on the total concentration of atoms in the target.

The theoretical density of the sputter target, ρ_(t), may be calculatedby the densities of the individual elements:ρ_(t)=[(C ₁ W ₁)+(C ₂ W ₂)+(C ₃ W ₃)]/[(C ₁ W ₁/ρ₁)+(C ₂ W ₂/ρ₂)+(C ₃ W₃/ρ₃)]where C₁, C₂, C₃ are the concentrations (in atomic %) of molybdenum, thesecond metal element and the third metal element, respectively, W₁, W₂,W₃ are the atomic masses of molybdenum, the second metal element and thethird metal element, respectively, and ρ₁, ρ₂, ρ₃ are the densities ofmolybdenum, the second metal element and the third metal element. Ingeneral, the theoretical density of a composition including n elementsmay be estimated by:ρ_(t)=[Σ(C _(i) W _(i))]/[Σ(C _(i) W _(i)/ρ_(i))]where the summations are from element i=1 to n, and C_(i), W_(i), andρ_(i) are respectively, the concentration, atomic mass, and density ofelement i.

The density of molybdenum, titanium, vanadium, chromium, niobium, andtantalum are about 10.2, 4.51, 6.11, 7.15, 8.57, and 16.4 g/cm³,respectively. The density of the sputter target may be greater thanabout 0.85 ρ_(t), preferably greater than about 0.90 ρ_(t), morepreferably greater than about 0.92 ρ_(t), even more preferably greaterthan about 0.94 ρ_(t), even more preferably greater than about 0.96ρ_(t), and most preferably greater than about 0.98 ρ_(t). The density ofthe sputter target is preferably less than about 1.00 ρt.

Texture of the Sputter Target

The texture of a sputter target may be determined by the orientation ofthe grains, such as the orientation of the grains of the first phase,the second phase, the third phase, or any combination thereof. Forexample, one or more of the phases may generally be oriented with<110>//ND, <111>//ND, <100>//ND, or a combination thereof. The rates atwhich the sputter target is sputtered (e.g., the deposition rate of asputtered film) may depend on the orientation of the grains. As such, insome aspects of the invention, the sputter target has a generallyuniform orientation. The orientation of the grains may be measured byelectron back scattered diffraction, using the method described in U.S.Patent Application Publication No. 2008/0271779A1 (Miller et al.,published Nov. 6, 2008) and International Patent Application PublicationNo. WO 2009/020619 A1 (Bozkaya et al., published Feb. 12, 2009), thecontents of which are both incorporated herein by reference in theirentirety. Thus measured, in a unit volume of a face centered cubic metalthe percentage of grains aligned within 15-degrees of <100>//ND may begreater than about 5%, greater than about 8%, greater than about 10.2%,greater than about 13%, or greater than about 15%, the percentage ofgrains aligned within 15-degrees of and <111>//ND may be greater thanabout 5%, greater than about 10%, greater than about 13.6%, or greaterthan about 15%, or greater than about 18%, or any combination thereof.Thus measured, the percentage of grains in a unit volume of a bodycentered cubic metal aligned within 15 degrees of <110>//ND may begreater than about 5%, greater than about 15%, 20.4% or greater thanabout 30%. The standard deviation of the texture gradient (e.g., the 100gradient, the 111 gradient, or both) may be less than about 4.0,preferably less than about 2.0, more preferably less than about 1.7,even more preferably less than about 1.5, even more preferably less thanabout 1.3, and most preferably less than about 1.1.

The variation in the orientation in the through-thickness direction mayalso be relatively low. For example, through-thickness texture gradientfor the texture components 100//ND, 111//ND, or both may be 6%/mm orless, preferably 4%/mm or less, and more preferably 2%/mm or less (asmeasured using the method described in International Patent ApplicationPublication No. WO 2009/020619 A1).

Deposited Molybdenum Containing Layer

As previously described, the sputter targets may be used to produce astructure having at least one molybdenum containing layer (e.g., adeposited layer, such as a deposited film layer) that comprisesmolybdenum, a second metal element, and a third metal element. Forexample, the sputter target may be used to produce a deposited layercomprising molybdenum, a second metal element selected from niobium andvanadium, and a third metal element different from the second metalelement, wherein the third metal element is selected from the groupconsisting of titanium, chromium, niobium, vanadium, and tantalum.Preferably the second metal element is niobium. Preferably the thirdmetal element is tantalum. Most preferably the second metal element isniobium and the third metal element is tantalum. The process ofdepositing a molybdenum containing layer on a substrate may include oneor any combination of the following: providing a particle, such as acharged particle, accelerating a particle, or impacting a sputter targetwith a particle, so that atoms are removed from a sputter target anddeposited onto a substrate. Preferred particles include atomic particlesand subatomic particles. By way of example, the subatomic particle maybe an ion. The sputter target may be employed to deposit a molybdenumcontaining layer including about 50 atomic % or more molybdenum, about0.5 atomic % or more of the second metal element, and about 0.5 atomic %or more of the third metal element, based on the total number of atomsin the layer. The concentration of molybdenum in the molybdenumcontaining layer may be about 60 atomic % or more, about 65 atomic % ormore, about 70 atomic % or more, or about 75 atomic % or more, based onthe total concentration of atoms in the molybdenum containing layer. Theconcentration of molybdenum in the molybdenum containing layer may beabout 98 atomic % or less, preferably about 95 atomic % or less, morepreferably about 90 atomic % or less, even more preferably about 85atomic % or less, and most preferably about 83 atomic % or less, basedon the total number of atoms in the molybdenum containing layer. Theratio of the concentration of molybdenum (in atomic %) in the depositedlayer to the concentration of molybdenum in the sputter target (inatomic %) may be about 0.50 or more, about 0.67 or more, about 0.75 ormore, about 0.80 or more, or about 0.9 or more. The ratio of theconcentration of molybdenum in the deposited layer to the concentrationof molybdenum in the sputter target may be about 2.00 or less, about 1.5or less, about 1.33 or less, about 1.25 or less, or about 1.11 or less.

The second metal element and the third metal element may eachindependently be present at a concentration about 0.1 atomic % or more,preferably about 1 atomic % or more, more preferably about 3 atomic % ormore, even more preferably greater 5 atomic % or more, and mostpreferably about 7 atomic % or more, based on the total concentration ofatoms in the molybdenum containing layer. The second metal element andthe third metal element may each independently be present at aconcentration of about 40 atomic % or less, about 35 atomic % or less,about 30 atomic % or less, about 25 atomic % or less, about 20 atomic %or less, or about 10 atomic % or less, based on the total concentrationof atoms in the molybdenum containing layer.

The total concentration of the second and third metal elements ispreferably about 5 atomic % or more, more preferably about 10 atomic %or more, and most preferably about 15 atomic % or more, based on thetotal concentration of atoms in the molybdenum containing layer. By wayof example, the total concentration of the second and third metalelements may be about 20 atomic % or more, based on the totalconcentration of atoms in the molybdenum containing layer. The total ofthe second metal element and the third metal element may be about 50atomic % or less, about 45 atomic % or less, about 40 atomic % or less,about 35 atomic % or less, about 30 atomic % or less, or about 25 atomic% or less, based on the total concentration of atoms in the molybdenumcontaining layer. The ratio of the total concentration of the second andthird metal elements (in atomic %) in the deposited layer to the totalconcentration of the second and third metal elements in the sputtertarget (in atomic %) may be about 0.50 or more, about 0.67 or more,about 0.8 or more, or about 0.9 or more. The ratio of the totalconcentration of the second and third metal elements (in atomic %) inthe deposit layer to the total concentration of the second and thirdmetal elements in the sputter target (in atomic %) may be about 2.00 orless, about 1.5 or less, about 1.25 or less, or about 1.11 or less.

The deposited molybdenum containing layer may be deposited (e.g., by aprocess that includes a step of sputtering the sputter target) onto asubstrate. As such, one aspect of the invention is a multi-layeredmaterial having at least a first deposited molybdenum containing layerincluding a first phase of the deposited layer having about 50 atomic %or more molybdenum, about 0.1 atomic % or more of the second metalelement and about 0.1 atomic % or more of the third metal element,wherein the second metal element is niobium or vanadium, and the thirdmetal element is a metal element different from the second metal elementand selected from the group consisting of titanium, chromium, niobium,vanadium, and tantalum. The first phase of the molybdenum containinglayer may comprise 60 volume % or more, 70 volume % or more, 80 volume %or more, 90 volume % or more, or 95 volume % or more of the molybdenumcontaining layer. The molybdenum containing layer may be substantiallyentirely the first phase of the deposited layer. The concentration ofthe molybdenum, the second metal element, and the third metal element inthe first phase of the deposited molybdenum containing layer may be anyof the above described concentrations for the molybdenum, the secondmetal element, and the third metal element in the molybdenum containinglayer.

The deposited layer may have an average grain size of about 5 to 10,000nm. The average grain size may be measured using microscopy (e.g.,scanning electron microscopy) of a surface normal to the thickness ofthe deposited layer. The size of an individual grain may be taken as thelargest dimension of the grain in the plane normal to the thickness ofthe deposited layer. The deposited layer (e.g., the first phase of thedeposited layer) preferably has a relatively small grain size (e.g., agrain size less than the grain size of the first phase of the sputtertarget, the second phase of the sputter target, the third phase of thesputter target, or any combination thereof). The first phase of thedeposited layer may have a grain size of about 5 nm or more, about 10 nmor more, about 20 nm or more, or about 50 nm or more. The first phase ofthe deposited film layer may have a grain size of about 10,000 nm orless. Preferably, the first phase of the deposited film layer has agrain size of about 1000 nm or less, about 500 nm or less, about 200 nmor less, or about 150 nm or less. The grains may be generally randomlyoriented, the grains may be generally aligned, or any combinationthereof. The grains may have any shape. For example, the grains may begenerally elongated. Preferably, the grains have a length to width ratiothat is less than about 100:1, more preferably less than about 30:1, andmost preferably less than about 10:1. The deposited layer may includegrains that have a generally large length to width ratio (e.g., greaterthan about 5:1 and grains that have a generally small length to widthratio (e.g., less than about 5:1, or less than about 2:1). The grainsmay have a generally uniform shape, such as a shape having a length towidth ratio less than about 3:1, less than about 2:1, or less than about1.5:1.

By way of example, FIG. 8A illustrates (without limitation) amicrostructure using secondary electron scanning electron microscopy ata magnification of about 50,000 of a deposited layer containing about 80atomic % molybdenum, about 10 atomic % of the second metal element, andabout 10 atomic % of the third metal element. With reference to FIG. 8A,the deposited layer may be substantially a single phase.

The thickness of the deposited molybdenum containing layer may varydepending on the functional requirements of the deposited layer. Withoutlimitation, the thickness of the deposited layer may be about 1 nm ormore, about 5 nm or more, about 10 nm or more, about 15 nm or more,about 20 nm or more, about 25 nm or more, about 30 nm or more, or about35 nm or more. The thickness of the deposited molybdenum containinglayer may be about 3 μm or less. Preferably, the thickness of thedeposited molybdenum containing layer is about 1 μm or less, morepreferably about 0.5 μm or less, even more preferably about 0.2 μm orless, even more preferably about 100 nm or less, and most preferablyabout 50 nm or less. Deposited layers having a thickness less than about1 nm are also contemplated.

FIG. 9 is a secondary electron scanning electron microscope micrograph(at a magnification of about 10,000) of the cross-section of a depositedlayer 90 containing about 80 atomic % molybdenum, 10 atomic % of thesecond metal element, and about 10 atomic % of the third metal elementon a substrate 92. As illustrated in FIG. 9, the deposited layer mayinclude a generally columnar microstructure. Other microstructures arealso contemplated.

The arrangement of the atoms in the deposited molybdenum containinglayer may be different from the arrangement of the atoms in the sputtertarget. For example, the deposited layer may include one or more firstalloy phases comprising i) at least 50 atomic % molybdenum and ii) atleast one of the second metal element and the third metal element. Assuch the deposited layer may be substantially free of (e.g., containless than 30 volume %, more preferably less than about 10 volume %, andmost preferably less than about 5 volume %, based on the total volume ofthe deposited layer) of phases comprising greater than about 90 atomic %molybdenum. Preferably, a majority of the second metal element in thedeposited layer is present in the one or more first alloy phases.Preferably, a majority or the third metal element in the deposited layeris present in the one or more first alloy phases.

Without limitation, the deposited layer may include a first phase thatcontains about 70% or more of the molybdenum in the deposited layer,preferably about 80% or more of the molybdenum in the deposited layer,more preferably about 90% or more of the molybdenum in the depositedlayer, and most preferably about 95% or more of the molybdenum in thedeposited layer. Without limitation, the deposited layer may include afirst phase that further contains about 70% or more of the second metalelement in the deposited layer, preferably about 80% or more of thesecond metal element in the deposited layer, more preferably about 90%or more of the second metal element in the deposited layer, and mostpreferably about 95% or more of the second metal element in thedeposited layer. Without limitation, the deposited layer may include afirst phase that further contains about 70% or more of the third metalelement in the deposited layer, preferably about 80% or more of thethird metal element in the deposited layer, more preferably about 90% ormore of the third metal element in the deposited layer, and mostpreferably about 95% or more of the third metal element in the depositedlayer.

The deposited layer may be deposited onto a substrate using a physicalvapor deposition process, such as a sputter deposition process (i.e., bysputtering). The deposition process may employ electric fields and/ormagnetic fields (preferably both) to remove atoms or groups of atomsfrom the sputter target using a gas (preferably an inert gas, such asargon) and to deposit at least a portion of the removed atoms onto asubstrate. The deposition process may employ one or more steps ofheating a sputter target, one or more steps of etching a sputter targetand/or substrate (for example to remove an oxide layer), one or moresteps of cleaning a sputter target and/or substrate, or any combinationthereof. The sputtering may be performed in a vacuum chamber at apressure less than atmospheric pressure. The pressure, temperature, andelectric fields may be chosen so that a plasma is formed. By way ofexample, the process may include sputtering at one or more pressures ofabout 100 Torr or less (about 13.3 kPa or less), preferably about 1000mTorr or less (about 133 Pa or less), more preferably about 100 mTorr orless (about 13.3 Pa or less), and most preferably about 20 mTorr or less(about 2.67 Pa or less). The process preferably includes sputtering atone or more pressures of about 0.1 mTorr or more (about 0.0133 Pa ormore), preferably about 1 mTorr or more (about 0.133 Pa or more), andmore preferably about 2 mTorr or more (about 0.267 Pa or more).

Optionally, the deposited layer may contain one or more second alloyphases, each containing about 50 atomic % or less molybdenum. Ifpresent, such optional second alloy phases preferably are present intotal concentration of about 40 volume % or less, more preferably about30 volume % or less, even more preferably about 20 volume % or less, andmost preferably about 10 volume % or less, based on the total volume ofthe deposited layer. Without limitation, the one or more second alloyphase of the deposited layer, if present, may each include at least 25atomic % of the second metal, at least 25 atomic % of the third metalelement, at least 50 atomic % of the second metal and third metal, basedon the total number of atoms in the second alloy phase, or anycombination thereof.

Without limitation, the deposited molybdenum containing layer mayfunction as a barrier layer, such as for performing the function ofsubstantially or entirely avoiding the migration of atoms of anunderlying layer into an overlying layer, substantially or entirelyavoiding the migration of atoms of an overlying layer into an underlyinglayer, or both. For example, the deposited molybdenum containing layermay be deposited over a first material (e.g., a first substratematerial) and then have a second material deposited over it. As such,the deposited molybdenum containing layer may prevent the migration(e.g., during an annealing step, during a forming step, or during use)of the one or more components (i.e., molecules or elements) of the firstmaterial into the second material, one or more components (i.e.,molecules or elements) of the second material into the first material,or both. The molybdenum containing layer may be interposed between asubstrate (e.g., a silicon substrate, or a glass substrate) and aconductive layer (such as a layer containing or consisting essentiallyof Cu, Al, Ag, Au, or any combination thereof). The thickness of thedeposited molybdenum containing layer (e.g., employed as a barrierlayer) may be about 1000 nm or less, about 500 nm or less, about 200 nmor less, about 100 nm or less, or about 50 nm or less. The thickness ofthe deposited molybdenum containing layer (e.g., employed as a barrierlayer) may be about 1 nm or more. The molybdenum containing layer mayinclude about 50 atomic % or more molybdenum (e.g., about 80 atomic %molybdenum), about 1 atomic % or more of a second metal element (e.g.,about 10 atomic niobium), and about 1 atomic % or more of a third metalelement (e.g., about 10 atomic % tantalum).

The materials may then be annealed, e.g., using an annealing temperatureof about 350° C. and an annealing time of about 30 minutes to determinethe barrier properties of the molybdenum containing layer. Themolybdenum containing layer may advantageously substantially if notentirely avoid the migration of components of the substrate layer intothe conductive layer and/or the molybdenum containing layer, reduce orprevent the migration of components of the conductive layer into thesubstrate layer and/or the molybdenum containing layer, or anycombination thereof. Without limitation, the molybdenum containing layermay advantageously reduce or prevent the formation of copper silicideafter annealing for about 30 minutes at about 350° C. For example, theconcentration of copper silicide may be below the level detectable byx-ray diffraction methods after annealing for about 30 minutes at about350° C. The deposited molybdenum containing layer may be employed toavoid changes in the electrical resistivity of the deposited layers(e.g., each layer, or the combination of the deposited layers) by anannealing process. Preferably the electrical resistivity changes by lessthan about 30%, more preferably by less than about 20%, and mostpreferably by less than 10%, after annealing for about 30 minutes at about 350° C. Such a generally constant electrical resistivity mayindicate that the molybdenum containing layer is preventing theformation of a silicide, such as copper silicide. The deposited layermay avoid the migration of copper atoms into a silicon layer, migrationof silicon atoms into a copper layer, or both. For example theconcentration of copper atoms at the surface of the silicon layer may beless than 1 atomic %, preferably less than about 0.1 atomic % and mostpreferably below the limit of detection as measured by Augerspectroscopy after annealing a structure comprising a deposition layerincluding molybdenum, the second metal element and the third metalelement on a clean silicon wafer, deposited by sputtering the sputtertarget using a magnetron, the deposition layer having a thickness ofabout 25 nm, and a layer of copper deposited over the deposition layer,the annealing at a temperature of about 350° C. and a time of about 30minutes. Under the same conditions, the concentration of silicon atomsat the surface of the copper layer may be about 1 atomic % or less,preferably about 0.1 atomic % or less, and most preferably below thelimit of detection as measured by Auger spectroscopy.

By way of illustration, FIG. 10A illustrates (without limitation) theAuger depth profile of a silicon substrate with a deposited molybdenumcontaining layer and a conductive copper layers. With reference to FIG.10A, the molybdenum containing layer may be interposed between thesilicon substrate and the conductive layer. As illustrated in FIG. 10A,the molybdenum containing layer may include about 50 atomic % or moremolybdenum (e.g., about 80 atomic % molybdenum), about 1 atomic % ormore of a second metal element (e.g., about 10 atomic niobium), andabout 1 atomic % or more of a third metal element (e.g. about 10 atomic% tantalum). The materials may then be annealed, e.g., using anannealing temperature of about 350° C. and an annealing time of about 30minutes to determine the barrier properties of the molybdenum containinglayer. As illustrated in FIG. 10B, the molybdenum containing layer mayadvantageously substantially if not entirely avoid the migration ofsilicon atoms from the substrate layer into the copper layer and/or themolybdenum containing layer, reduce or prevent the migration of copperatoms from the conductive layer into the silicon layer and/or themolybdenum containing layer, or any combination thereof. Withoutlimitation, the molybdenum containing layer may advantageously reduce orprevent the formation of copper silicide after annealing for about 30minutes at about 350° C.

The deposited molybdenum containing layer may be characterized by one orany combination of the following: a generally good adhesion to glass(e.g., at least 2B, at least 3B, at least 4B, or at least 5B rating whentested according to ASTM B905-00), a generally good adhesion to silicon(e.g., at least 2B, at least 3B, at least 4B, or at least 5B rating whentested according to ASTM B905-00), a generally good adhesion (e.g., atleast 2B, at least 3B, at least 4B, or at least 5B rating when testedaccording to ASTM 8905-00) to a conductive layer, such as a layercontaining or consisting essentially of copper, aluminum, chromium, orany combination thereof ability to prevent copper silicide formationwhen the molybdenum containing deposited layer (e.g., having a thicknessof about 200 nm or less, preferably having a thickness of about 35 nm orless, and more preferably having a thickness of about 25 nm or less) isplaced between and in contact with Si and Cu and annealed for about 30minutes at about 350° C.; or an electrical resistivity less than about60, preferably less than about 45, more preferably less than about 35μΩ·cm for a film having a thickness of about 200 nm.

The deposited molybdenum containing layer may have a relatively lowelectrical resistivity. For example, the electrical resistivity of themolybdenum containing layer may be less than the electrical resistivityof a deposited layer of the same thickness consisting of 50 atomic %molybdenum and 50 atomic % titanium.

Preferably the deposited molybdenum containing layer has a generally lowelectrical resistivity. For example, the electrically resistivity (asmeasured by a four-point probe on a film having a thickness of about 200nm) of the deposited molybdenum containing layer preferably is of about75 μΩ·cm or less, more preferably about 60 μΩ·cm or less, even morepreferably about 50 μΩ·cm or less, even more preferably about 40 μΩ·cmor less, even more preferably about 30 μΩ·cm or less, even morepreferably about 28 μΩ·cm or less, even more preferably about 25 μΩ·cmor less, and most preferably about 20 μΩ·cm or less. Preferably, theelectrically resistivity of the deposited molybdenum containing layer isabout 5 μΩ·cm or more. It will be appreciated that the electricalresistivity of the deposited molybdenum containing layer may also beless than about 5 μΩ·cm. The deposited molybdenum containing layerpreferably has a generally uniform electrical resistivity. For examplethe ratio of the standard deviation of the electrical resistivity to theaverage electrical resistivity (measured on a 200 nm thick layerdeposited on a 76.2 mm diameter silicon wafer) preferably is about 0.25or less, more preferably about 0.20 or less, even more preferably about0.12 or less, even more preferably about 0.10 or less, and mostpreferably about 0.06 or less.

Etching of the Deposited Molybdenum Containing Layer

After depositing the molybdenum containing layer it may be desirable toat least partially etch the molybdenum containing layer. By way ofexample, a step of etching may be employed so that a portion of a layerunderlying the molybdenum containing layer becomes exposed (e.g. untilanother layer, such as a conductive layer, is deposited). It may bedesirable for the etch rate of the molybdenum containing layer to begenerally high so that short etching times may be employed, so thatmilder etching chemicals may be used, so that thicker molybdenumcontaining layers may be employed, or any combination thereof.

The step of etching may include a step of etching with a chemical orsolution capable of removing some or all of the deposited molybdenumcontaining layer. More preferably, the etching step includessufficiently etching the molybdenum layer so that a layer below themolybdenum layer, such as a substrate layer, is at least partiallyexposed after the etching step. The etching step may employ a solutionor chemical that includes an acid. For example, the etching step mayemploy a solution or chemical having a pH of about 8 or more, a pH ofabout 10 or more, or a pH of about 12 or more. The etching step mayemploy a solution or chemical that includes a base. For example, theetching step may employ a solution or chemical having a pH of about 6 orless, a pH of about 4 or less, or a pH of about 2 or less. The etchingstep may employ a solution or chemical that is generally neutral.Generally neutral solutions or chemicals have a pH greater than about 6,a pH of about 6.5 or more, a pH or about 6.8 or more, or a pH of about 7or more. Generally neutral solutions or chemicals also have a pH lessthan about 8, a pH of about 7.5 or less, a pH or about 7.2 or less, or apH of about 7 or less.

The etching process may employ one or more acids. Exemplary acids thatmay be used include nitric acid, sulfuric acid, hydrochloric acid, andcombinations thereof. The etching process may employ a sulfate.Exemplary sulfates include those described in U.S. Pat. No. 5,518,131,column 2, lines 3-46 and column 2, lines 62 to column 5, line 54,expressly incorporated herein by reference, such as ferric sulfate andferric ammonium sulfate. The etching process may employ a solutionincluding ferricyanide ions, chromate ions, dichromate ions, ferricions, or any combination thereof. For example, the etching process mayemploy one or more ions containing solutions described in U.S. Pat. No.4,747,907, column 1, line 66 to column 8, line 2, incorporated byreference herein. A particularly preferred solution for etching themolybdenum containing layer is a solution including ferricyanide ions.

Preferably, the process of preparing the multi-layered structureincludes a step of etching the molybdenum containing layer at a rate ofabout 75 nm/min or more, more preferably about 100 nm/min or more, evenmore preferably about 150 nm/min or more, even more preferably about 200nm/min or more, even more preferably about 300 nm/min or more, even morepreferably about 400 nm/min or more, and most preferably about 500nm/min or more. The etching step may employ any etching solution capableof etching the molybdenum containing layer. The etching step may employa ferricyanide solution at one or more of the above rates.

The deposited molybdenum containing layer may have a relatively highetch rate in ferricyanide solution at 25° C., such as an etch rategreater than the etch rate of a deposited layer consisting of 50 atomic% molybdenum and 50 atomic % titanium using the same etching conditions.For example, the etch rate of the deposited molybdenum containing layerin ferricyanide solution at 25° C. may be about 75 nm/min or more,preferably about 100 nm/min or more, more preferably about 150 nm/min ormore, even more preferably about 150 nm/min or more, even morepreferably about 200 nm/min or more, even more preferably about 300nm/min or more, even more preferably about 400 nm/min or more, and mostpreferably greater than about 500 nm/min. The etch rate of the depositedmolybdenum containing layer in ferricyanide solution at 25° C. ispreferably about 10,000 nm/min or less, and most preferably about 2,000nm/min or less.

Process

In general, the targets (or preformed structures, such as blocks forassembling into a target) may be made using metal powder startingmaterials. One such approach includes consolidating such powders, suchas by heat, pressure, or both. For example, powders may be compacted andsintered, cold isostatically pressed, hot isostatically pressed, or anycombination thereof.

The process for making the target may include one or any combination ofthe steps disclosed by Gaydos et al. in U.S. Patent ApplicationPublication Nos. 2007/0089984A1, published on Apr. 26, 2007 andUS2008/0314737, published on Dec. 25, 2008, the contents of which areincorporated herein by reference in their entirety.

The process for making the sputter targets may include a step ofproviding at least a first powder including about 50 atomic % or moremolybdenum, a second powder including about 50 atomic % or more of asecond metal element, and a third powder including about 50 atomic % ormore of a third metal element, wherein the second metal element isniobium or vanadium, and the third metal element is a different elementfrom the second metal element and selected from the group consisting oftitanium, chromium, niobium, vanadium, and tantalum. The individualpowders (e.g., the first powder, the second powder and the third powder)may be blended together to produce a blended powder. The process mayoptionally include one or more step of consolidating the blended powderto produce a consolidated powder. The blending step preferably uses atemperature sufficiently low so that powder does not fuse together. Theblending preferably uses a sufficient blending time and speed so thatthe first powder, the second powder, and the third powder becomegenerally randomly distributed. By way of example, the blending may beperformed at a temperature below about 100° C. (e.g., at about 25° C.)in a V-blender.

Preferably the process of preparing the sputter target is free of a stepof mixing (e.g., mechanically mixing) two or more of the first powder,the second powder, and the third powder at a temperature at which analloy is formed. For example, the process may be free of a step ofmixing two or more of the first powder, the second powder, and the thirdpowder at a temperature of about 550° C. or more, about 700° C. or more,about 900° C. or more, about 1100° C. or more, about 1200° C. or more,or about 1500° C. or more.

The process may include one or more steps of encapsulating the blendedpowder or the consolidated powder to produce an encapsulated powderand/or one or more steps of compacting while heating the encapsulatedpowder to produce a first target plate.

Preferably, the process of preparing the sputter target includes one ormore steps of pressing the powders or the consolidated powders to form atarget plate (e.g., a block or blank) by pressing at a predeterminedtime, at a predetermined pressing pressure, and for a predeterminedpressing temperature sufficiently high so that the powders fusetogether, so that the density of the material increases to at about 0.85ρ_(t) or more, where ρ_(t) is the theoretical density. The target plate(e.g., the block or blank) may be further processed (e.g., as describedhereinafter) to form a sputter target. As such, it will be recognizedthat target plates and methods for producing target plates are includedin the teachings herein. Various compacting methods are known in theart, including, but not limited to, methods such as inert gas uniaxialhot pressing, vacuum hot pressing, and hot isostatic pressing, and rapidomnidirectional compaction, the Ceracon™ process. The pressing steppreferably includes a step of hot isostatically pressing the powder.Preferably the predetermined temperature is about 800° C. or more, morepreferably about 900° C. or more, even more preferably about 1000° C. ormore, even more preferably about 1100° C. or more, and most preferablyabout 1200° C. or more. Preferably the predetermined temperature isabout 1700° C. or less, more preferably about 1600° C. or less, evenmore preferably about 1500° C. or less, even more preferably about 1400°C. or less, and most preferably about 1300° C. or less. Thepredetermined pressing time may be about 1 minute or more, preferablyabout 15 minutes or more, and more preferably about 30 minutes or more,the predetermined time preferably is about 24 hours or less, morepreferably about 12 hours or less, even more preferably about 8 hours orless, and most preferably about 5 hours or less. The predeterminedpressing pressure may be about 5 MPa or more, about 20 MPa or more,about 50 MPa or more, or about 70 MPa or more. The predeterminedpressure may be about 1000 MPa or less, preferably about 700 MPa orless, more preferably about 400 MPa or less and most preferably about250 MPa or less.

The process for making a target may optionally include a step of bonding(two or more target plates (e.g., a first target plate and a secondtarget plate) to produce a bonded target plate. By way of example, thestep of bonding may be a step of edge bonding. The bonding process maybe a diffusion bonding process. A bonding step may be advantageous inproducing targets having a relatively large area (e.g., a length greaterthan about 67 inches (1702 mm), or greater than about 84 inches (2134mm) and a width greater than about 55 inches (1397 mm), or greater thanabout 70 inches (1778 mm).

As taught herein, in a preferred aspect of the invention, a target plateformed by pressing may be capable of being rolled so that the length ofthe target plate is increased, so that the width of the target plate isincreased, or both. As such, the process of forming the sputter targetmay be substantially free of, or even entirely free of a step of abonding (e.g. edge bonding) two or more target plates. It will beappreciated that one or more steps of rolling the target plate may beemployed. By rolling the target plate, the need for large molds and/orlarge presses (such as molds and/or presses that are at least about thesize of the final sputter target) may be avoided. One or more steps ofrolling may be advantageous in producing sputter targets having arelatively large area (e.g., a length greater than about 67 inches (1702mm), or greater than about 84 inches (2134 mm) and a width greater thanabout 55 inches (1397 mm), or greater than about 70 inches (1778 mm).

Forging

The process for making the target may optionally include one or moresteps of forging. If employed, the forging step may include hot forging(e.g., at a temperature above a recrystallization temperature of thetarget material). Suitable forging methods that may be used includepress forging, upset forging, automatic hot forging, roll forging,precision forging, induction forging, and any combination thereof.Without limitation, the forging process may employ rotary axial forgingas described for example in International Patent Application PublicationNo. WO2005/108639 A1 (Matera et al., published on Nov. 17, 2005), thecontents of which are incorporated herein by reference in its entirety.A rotary axial forging process may employ a rotary axial forging machinesuch as one described in Paragraph 0032 of WO2005/108639 A1.

Reducing/Eliminating Variation in Texture

The process for making the target may include a step of tilt rolling orother asymmetric rolling, using a method or apparatus such as describedin International Patent Application No. WO 2009/020619 A1 (Bozkaya etal, published on Feb. 12, 2009), the contents of which are incorporatedherein by reference in its entirety.

Applications

The sputter targets may be employed in producing one or more layers(e.g., as one or more barrier layers) in an electrode substrate of aflat panel display or a photovoltaic cell. Examples of flat paneldisplays which may advantageously employ the sputter targets of thepresent invention include a liquid crystal display (e.g., an activematrix liquid crystal display, such as a thin film transistor-liquidcrystal display (i.e., a TFT-LCD)), a light emitting diode, a plasmadisplay panel, a vacuum fluorescent display, a field emission display,an organoluminescent display, an electroluminescent displays, and anelectro-chromic displays.

Devices that may include molybdenum containing films prepared from thesputter targets include computer monitors, optical disks, solar cells,magnetic data storage, optical communications, decorative coatings, hardcoatings, glass coatings including WEB coatings, cameras, videorecorders, video games, cell phones, smartphones, touch screens, globalpositioning satellite devices, video scoreboards, video billboards,other display panels, or the like.

With reference to FIG. 11, one such device may include a multi-layeredstructure 102. The multi-layered structure includes two or more layersincluding a substrate layer 104 and a deposited molybdenum containinglayer 106. The substrate layer may be formed of a glass, asemiconductor, a metal, a polymer, or any combination thereof. It willbe appreciated that the substrate layer may include a plurality ofmaterials. A preferred substrate layers includes or consists essentiallyof glass. Another preferred substrate layer includes or consistsessentially of silicon. The multi-layered structure includes one or moredeposited layers 106. The deposited layer 106 may be formed by a sputtermethod according to the teachings herein, may be formed from a sputtertarget according to the teachings herein, or both. The deposited layer106, may be a thin film. The deposited layer may have a thickness lessthan the thickness of the substrate layer 102. The deposited layer mayhave a thickness less than about 1 μm, even more preferably less thanabout 200 nm, even more preferably less than about 100 nm, and mostpreferably less than about 50 nm. The deposited layer 106 may bedeposited onto the substrate 104, or the deposited layer 106 may bedeposited onto one or more intermediate layers (not shown) interposedbetween the substrate layer 104 and the deposited layer 106. Themulti-layered structure 102 may also include one or more conductivelayers 108. The conductive layer 108 may have an electrical conductivitygreater than the substrate layer 104, greater than the deposited layer106, or preferably greater than both the substrate layer 104 and thedeposited layer 106. The deposited layer 106 preferably is interposedbetween the substrate layer 104 and a conductive layer 108. For example,a deposited layer 106 may include a first surface at least partially incontact with the substrate layer 104, and an opposing surface at leastpartially in contact with a conductive layer 108. As such, the depositedlayer 106 may be a barrier layer that reduces or prevents the diffusionof atoms between a conductive layer 108 and a substrate layer 102.

Test Methods

Adhesion

Adhesion is measured using an adhesion tape test according to ASTMB905-00. A rating of 5B indicates good adhesion and that the depositedlayer is not removed by the tape.

Deposition Rate

Deposition rate is determined by measuring the thickness of thedeposited layer (in units of nm) and dividing by the deposition time (inunits of minutes).

Etch Rate

The etch rate (in units of μm/min) is measured as the rate of change inthickness of the deposited layer when immersed in a ferricyanidesolution at 25° C.

Electrical Resistivity

The sheet resistance of the deposited films is measured using afour-point probe. Two samples are measured for each depositioncondition. The resistivity is then calculated by the geometry of thetest sample.

Microstructure of Deposited Films

The microstructure of the deposited films is obtainable using scanningelectron microscopy. A JEOL JSM-7000F field emission electron microscopethat can measure backscattered electrons and secondary electrons is usedin the examples.

Microstructure of the Sputter Targets.

The microstructure of the sputter targets is obtainable using scanningelectron microscopy. An ASPEX Personal Scanning Electron Microscope isemployed. The working distance is about 20 mm and the accelerationvoltage is about 20 keV. The secondary electron detector isEverhart-Thornley type. The images are also obtained of thebackscattered electrons. The electron microscope is also employed formeasurement of energy dispersive x-ray spectroscopy using a spot size ofabout 1 μm. Samples for electron microscopy of the sputter target areprepared by sectioning with an abrasive cutoff wheel, mounting thesection in a polymeric material, rough grinding with SiC papers withprogressively finer grits, final polishing with a diamond paste and thenwith an Al₂O₃, SiO₂ suspension.

X-Ray Diffraction Measurements

X-ray diffraction studies are performed using a Phillips XPert Pro X-raydiffractometer.

Any numerical values recited herein include all values from the lowervalue to the upper value in increments of one unit provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent or a value of a process variable such as, for example,temperature, pressure, time and the like is, for example, from 1 to 90,preferably from 20 to 80, more preferably from 30 to 70, it is intendedthat values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. areexpressly enumerated in this specification. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner.

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints.

The disclosures of all articles and references, including patentapplications and publications are incorporated by reference for allpurposes. The term “consisting essentially of” to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist essentially of orconsist of the elements, ingredients, components or steps.

Plural elements, ingredients, components or steps can be provided by asingle integrated element, ingredient, component or step. Alternatively,a single integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps.

It is understood that the above description is intended to beillustrative and not restrictive. Many embodiments as well as manyapplications besides the examples provided will be apparent to those ofskill in the art upon reading the above description. The scope of theinvention should, therefore, be determined not with reference to theabove description, but should instead be determined with reference tothe appended claims, along with the full scope of equivalents to whichsuch claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated by reference for all purposes. The omission in thefollowing claims of any aspect of subject matter that is disclosedherein is not a disclaimer of such subject matter, nor should it beregarded that the inventors did not consider such subject matter to bepart of the disclosed inventive subject matter.

EXAMPLES Examples 1-13 Molybdenum/Niobium/Tantalum

Example 1 illustrates a sputter target including molybdenum, niobium andtantalum. Examples 2-13 illustrate deposited films prepared from thesputter target of Example 1.

Example 1

Example 1 is a sputter target that is prepared by first blendingmolybdenum powder having a particle size of about 3-4 μm, tantalumpowder having a particle size of about 45-90 μm, and niobium powderhaving a particle size of about 10-45 μm to form a powder blend havingabout 80 atomic % molybdenum, about 10 atomic % niobium, and about 10atomic % tantalum. The blending is done in a V-blender for about 20minutes to obtain a homogeneous mixture of the three different powders.The resulting powder blend is then consolidated by uniaxially pressingwith an applied force of about 340,000 kg into pellets having a diameterof about 95 mm (i.e., a pressure of about 470 MPa) at a temperature ofabout 23° C. The pressed pellet is then encapsulated in a can made oflow carbon steel and hot isostatically pressed at a temperature of about1325° C. and a pressure of about 100 to about 120 MPa for about 4 hours.Thus prepared, Example 1 has a density which is greater than about 94%of the theoretical density. The consolidated material is then removedfrom the can and machined to a diameter of about 58.4 mm and a thicknessof about 6.4 mm.

The target includes at least one first phase containing greater than 50atomic % molybdenum, at least one second phase containing greater than50 atomic % niobium, and at least one third phase containing greaterthan about 50 atomic % tantalum. A scanning electron micrograph of thesputter target using secondary electrons is illustrated in FIG. 1.Scanning electron micrographs of the sputter target using backscatteredelectrons are illustrated in FIGS. 2, 3A, 4A, 5A, 6A, and 7A. Asillustrated in these figures, the sputter target may have a morphologyincluding a continuous phase of molybdenum 16 a discrete phase oftantalum 12 (indicated by the light regions), and a discrete phase ofniobium 14 (indicated by the dark regions). The sputter target is alsoanalyzed using X-ray absorption spectroscopy for elemental analysis indifferent regions of the target. As illustrated in FIG. 3B, the sputtertarget includes a phase consisting essentially of molybdenum. Asillustrated in FIG. 4B, the sputter target includes a phase thatconsists essentially of niobium. As illustrated in FIG. 5B, the sputtertarget includes a region that consists essentially of tantalum. Asillustrated in FIG. 6B, the sputter target includes a region thatconsists essentially of an alloy of molybdenum and niobium. Asillustrated in FIG. 7B, the sputter target includes a region thatconsists essentially of an alloy of molybdenum and tantalum.

As illustrated in FIGS. 1-7, the majority of the sputter target may bethe first phase (i.e., the phase containing 50 atomic % or moremolybdenum) and the first phase may be a continuous phase. Without beingbound by theory, it is believed that the alloy phases (e.g., themolybdenum/niobium alloy phase and the molybdenum/tantalum alloy phase)are formed during the hot isostatic pressing step by diffusion of themetal elements (e.g., diffusion of the molybdenum atoms into niobiumdomains and into tantalum domains).

Examples 2-13

Examples 2-13 illustrate a method that includes steps of sputtering athin film layer using a sputter target as taught herein onto a substrate(e.g., a silicon-containing substrate, or a glass-containing substrate).Sputtering may be performed using a magnetron. In general, sputteringwill occur for about 1 to about 240 minutes (preferably about 1 to about40 minutes), under conditions of vacuum from about 1 to about 100 mTorrpressure (preferably from about 2 to about 20 mTorr pressure), and aspacing between the substrate and the sputter target of about 5 to 300mm (preferably about 20 to about 150 mm. The resulting structure willhave characteristics consistent with examples 2-13 herein.

Examples 2-13 are prepared by placing the sputter target of Example 1into a magnetron sputter deposition chamber using the conditionsdescribed in Tables 1A and 1B. The substrate is either a silicon wafer(100) orientation, or Corning 1737 glass. Prior to deposition, thesubstrate is cleaned by successive rinsing in ultrasonic baths ofacetone and ethyl alcohol. The substrates are then dried by blowingnitrogen gas. The substrates are next loaded into the deposition chamberalong with the sputter target. The target is sputter cleaned with anargon flow of at a pressure of about 5 mTorr at 200 W DC for about 10minutes. During the cleaning of the target, a shutter is placed in frontof the target to prevent deposition onto the substrate.

When using the glass substrate, the substrate is etched by sputtering at60 mTorr for 30 minutes to remove possible contamination on thesubstrate surface.

After the sputter cleaning of the target, the shutter is removed and thetarget material is sputtered onto a substrate using 300 W, directcurrent, with the substrate at 0V, grounded. The spacing between thesubstrate and the target is maintained at about 121 mm. Sputtering timesof about 5 minutes and about 30 minutes, and chamber pressures of about3, about 5 and about 8 mTorr are employed as shown in Tables 1A and 1B.

TABLE 1A Deposition conditions using the sputter target of Example 1target on silicon substrate. Example Number EX. 2 EX. 3 EX. 4 EX. 5 EX.6 EX. 7 Sputter Target EX. 1 EX. 1 EX. 1 EX. 1 EX. 1 EX. 1 Substrate-Siwafer 100 yes yes yes yes yes yes Substrate-Corning 1737 glass ChamberPressure, mTorr 3 3 5 5 8 8 Deposition time, min 5 30 5 30 5 30Thickness, μm 0.2 1.0 0.2 1.1 0.2 1.3 Etch rate, nm/min 447 484 502

TABLE 1B Deposition conditions using the sputter target of Example 7Atarget on glass substrate. Example Number EX. 8 EX. 9 EX. 10 EX. 11 EX.12 EX. 13 Sputter Target EX. 1 EX. 1 EX. 1 EX. 1 EX. 1 EX. 1Substrate-Si wafer 100 Substrate-Corning yes yes yes yes yes yes 1737glass Chamber Pressure, 3 3 5 5 8 8 mTorr Deposition time, 5 30 5 30 530 min Resistivity, μΩ · cm 18.0 17.3 19.4 17.9 20.1 19.5

FIG. 8A is a secondary electron scanning electron micrograph at amagnification of about 50,000 that illustrates the surface of thedeposited layer of Example 3 (deposited using a deposition pressure ofabout 3 mTorr and a deposition time of about 30 minutes). The morphologyof the deposited layer consists essentially of a single alloy phasecontaining about 80 atomic % molybdenum, about 10 atomic % niobium andabout 10 atomic % tantalum. As illustrated in FIG. 8A, the alloy ofExample 3 has an average grain size of about 49 nm. FIG. 8B is asecondary electron scanning electron micrograph at a magnification ofabout 50,000 that illustrates the surface of the deposited layer ofExample 7 (deposited using a deposition pressure of about 8 mTorr and adeposition time of about 30 minutes). The morphology of the depositedlayer consists essentially of a single alloy phase containing about 80atomic % molybdenum, about 10 atomic % niobium and about 10 atomic %tantalum. As illustrated in FIG. 8B, the alloy has an average grain sizeof about 62 nm.

FIG. 9 is a secondary electron scanning electron micrograph at amagnification of about 30,000 that illustrates the cross-section of thedeposited layer of Example 7. The deposited layer has a columnarmorphology.

In Examples 2-13, the deposited layers are deposited at a depositionrate of about 33 to about 41 nm/min. Samples prepared with a depositiontime of about 5 minutes have a thickness of about 200 nm. Samplesprepared with a deposition time of about 30 minutes have a thickness ofabout 900 to about 1300 nm. The adhesion to the glass substrate of theExample 10 prepared at a pressure of about 5 mTorr is about 48. Theadhesion to the glass substrate of the Examples 8 and 12 prepared at apressure of 3 and 8 mTorr respectively is about 5B. The adhesion to thesilicon substrate of Example 2, 4 and 6 prepared at pressure of 3, 5 and8 mTorr respectively is about 5B.

The electrical resistivity of the deposited layers is given in Table 1Bfor Examples 8-13. The average electrical resistivity of the depositedlayer on the glass substrate is about 19.2 μΩ·cm for the layers having athickness from about 100 to about 200 nm and about 18.2 μΩ·cm for thesamples having a thickness greater than about 0.9 μm. The uniformity ofthe electrical resistivity is measured on Example 4, by measuring theelectrical resistivity at multiple locations on the 3″ wafer. Theuniformity of the electrical resistivity is the ratio of the standarddeviation of the electrical resistivity to the average electricalresistivity. The uniformity of the electrical resistivity of Example 4is about 0.07.

The etch rate of the deposited layers in ferricyanide solution forExamples 3, 5, and 7 are measured at 25° C. The etch rates aredetermined by dividing the change in thickness by the etching time. Theetch rates, in units of nm/min are given in Table 1A. The average etchrate for the films prepared with the Example 1 sputter target is about478 nm/min.

Example 14

Example 14 is prepared by depositing a 35 nm molybdenum containing layerfrom the Example 1 sputter target onto a silicon substrate followed bythe depositing of a copper (Cu) layer having a thickness of about 300 nmonto the molybdenum containing layer. The composition depth profile ofthe multilayered material is measured using Auger depth profileanalysis. The sample is then annealed for 30 minutes at 350° C. and theAuger depth profile analysis is repeated. FIG. 10A Illustrates the Augerdepth profile for copper (Cu), molybdenum (Mo), niobium (Nb), tantalum(Ta), oxygen (O), and silicon (Si) before annealing. FIG. 10Billustrates the Auger depth profile after annealing. FIG. 10Cillustrates the Auger depth profile for Cu, Mo, Nb, Ta, O and Si, beforeand after the annealing near the interfaces between the molybdenumcontaining layer and both the silicon substrate and the copper layer. Asseen in FIGS. 10A, 10B and 10C, the composition profiles for Cu, Mo, Nb,Ta, O, and Si, are about the same before and after the annealing step.The molybdenum containing layer acts as a barrier to reduce and/orprevent the migration of Cu into the Si substrate and Si into the Culayer. X-ray analysis of the sample after annealing shows that there isno detectable copper silicide. This illustrates the ability of theMo—Nb—Ta deposited film from the Example 1 sputter target to prevent theformation of copper silicide after annealing for 30 minutes at 350° C.The electrical resistivity of the copper layer is about 1.7 μΩ·cm beforeannealing and about 1.7 μΩ·cm after annealing. The generally constantelectrical resistivity of the copper layer further indicates that themolybdenum containing layer is preventing the formation of coppersilicide.

Examples 15-16 Molybdenum (50%) and Titanium (50%) Example 15

Comparative Example 15 is a sputter target including about 50 atomic %molybdenum and about 50 atomic % titanium. The sputter target isprepared using the method described for Example 1, except only titaniumand molybdenum particles are used at an atomic ratio of 50:50 of Mo:Ti,the target is hot isostatically pressed at a temperature of about 1325°C. and a pressure of about 100 to about 120 MPa for about 4 hours.

Example 16

Example 16 is a 200 nm thick film deposited on a glass substrate usingthe method of Example 10, except the sputter target of Example 15 isused. The deposition rate is about 102.6 nm/min. The electricalresistivity of the 200 nm thick film is about 79.8 μΩ·cm. The adhesionof the deposited layer to glass is about 5B. The etch rate of thedeposited layer is about 77 nm/min. The deposited layer has a columnarmorphology.

Examples 17-25 Molybdenum/Titanium/Tantalum

Example 17 illustrates a sputter target including molybdenum, titanium,and tantalum, and Examples 18-25 illustrate deposited films preparedfrom the sputter target.

Example 17 is a sputter target that is prepared by first blendingmolybdenum powder having a particle size of about 3-4 μm, titaniumpowder having a particle size of about 10-45 μm, and tantalum powderhaving a particle size of about 45-90 μm to form a powder blend havingabout 80 atomic % molybdenum, about 10 atomic % titanium, and about 10atomic % tantalum. The blending is done in a V-blender for about 20minutes to obtain a homogeneous mixture of the three different powders.The resulting powder blend is then consolidated by uniaxially pressingwith an applied force of about 340,000 kg into pellets having a diameterof about 95 mm (i.e., a pressure of about 470 MPa) at a temperature ofabout 23° C. The pressed pellet is then encapsulated in a can made oflow carbon steel and hot isostatically pressed at a temperature of about1325° C. and a pressure of about 100 to about 120 MPa for about 4 hours.Thus prepared, Example 17 has a density which is greater than about 94%of the theoretical density. The consolidated material is then removedfrom the can and machined to a diameter of about 58.4 mm and a thicknessof about 6.4 mm.

Examples 18-25 are prepared by placing the sputter target of Example 17into a magnetron sputter deposition chamber using the conditionsdescribed in Table 2. The substrate is either a silicon wafer (100)orientation, or Corning 1737 glass. Prior to deposition, the substrateis cleaned by successive rinsing in ultrasonic baths of acetone andethyl alcohol. The substrates are then dried by blowing nitrogen gas.The substrates are next loaded into the deposition chamber along withthe sputter target. The target is sputter cleaned with an argon flow ofat a pressure of about 5 mTorr at 200 W DC for about 10 minutes. Duringthe cleaning of the target, a shutter is placed in front of the targetto prevent deposition onto the substrate.

When using the glass substrate, the substrate is etched by sputtering at60 mTorr for 30 minutes to remove possible contamination on thesubstrate surface.

After the sputter cleaning of the target, the shutter is removed and thetarget material is sputtered onto the substrate using 200 W, directcurrent, with the substrate at 0V, grounded. The spacing between thesubstrate and the target is maintained at about 76 mm. Sputtering timesof 3 minutes and 30 minutes, and chamber pressures of 5 and 8 mTorr areemployed as shown in Table 2.

TABLE 2 Deposition Conditions for Mo—Ti—Ta sputter targets ExampleNumber EX. 18 EX. 19 EX. 20 EX. 21 EX. 22 EX. 23 EX. 24 EX. 25 SputterTarget EX. 17 EX. 17 EX. 17 EX. 17 EX. 17 EX. 17 EX. 17 EX. 17Substrate-Si wafer yes yes yes yes 100 Substrate-Corning yes yes yes yes1737 glass Chamber 5 5 8 8 5 5 8 8 Pressure, mTorr Deposition time, 3 303 30 3 30 3 30 min

The deposition rate of the Example 17 target onto the substrates isabout 62.4 nm/hr using the conditions of Examples 18-25. The depositedfilms contain about 80 atomic % molybdenum, about 10 atomic % titaniumand about 10 atomic % tantalum.

The average grain size of the deposited layer of Examples 23 and 25 aremeasured using secondary electron scanning electron micrograph at amagnification of about 50,000 of the surface of the deposited layer. Theaverage grain size of Examples 20 and 21 are 125 nm and 89 nmrespectively.

The thin films (having a thickness of about 200 nm and prepared with adeposition time of about 5 minutes) deposited by the Example 17 sputtertarget have an electrical resistivity of about 26.5 μΩ·cm and the thickfilms (having a thickness greater than about 1 μm and prepared with adeposition time of about 30 minutes) have an electrical resistivity ofabout 22.6 μΩ·cm.

When etched in ferricyanide solution at about 25° C., the depositedfilms form Example 17 have an average etch rate of about 61 nm/min. Theadhesion of the deposited film to the glass substrate varied from about2B to about 5B, and the adhesion of the deposited film to the siliconsubstrate is about 5B.

Example 26 Molybdenum/Niobium/Titanium

The sputter target of Example 26 is prepared using the method of Example1 except the tantalum powder is replaced with titanium powder having aparticle size of about 10-45 μm. Deposited films are then prepared usingthe methods of Examples 2-13, except the sputter target includingmolybdenum, niobium, and titanium is employed. The deposited films havean etch rate of about 497 nm/min. The deposited films have an adhesionto glass of about 5B. The deposited films have an adhesion to silicon ofabout 5B. The deposited films have a grain size of about 51-98 nm. Thedeposited films have an electrical conductivity of about 30.9 μΩ·cm (for200 nm thick films) and about 20.0 μΩ·cm (for 1 μm thick films).

Example 27 Molybdenum/Vanadium/Titanium

The sputter target of Example 27 is prepared using the method of Example1 except the tantalum powder is replaced with titanium powder having aparticle size of about 10-45 μm and niobium powder is replaced withvanadium powder having a particle size of about 10-45 μm. Depositedfilms are then prepared using the methods of Examples 2-13, except thesputter target including molybdenum, vanadium, and titanium is employed.The deposited films have an etch rate of about 270 nm/min. The depositedfilms have an adhesion to glass of about 5B. The deposited films have anadhesion to silicon of about 5B. The deposited films have a grain sizeof about 49-72 nm. The deposited films have an electrical conductivityof about 32.5 μΩ·cm (for 200 nm thick films) and about 28.5 μΩ·cm (for 1μm thick films).

Example 28 Molybdenum/Vanadium/Tantalum

The sputter target of Example 28 is prepared using the method of Example1 except the niobium powder is replaced with vanadium powder having aparticle size of about 10-45 μm. Deposited films are then prepared usingthe methods of Examples 2-13, except the sputter target includingmolybdenum, vanadium, and tantalum is employed. The deposited films havean etch rate of about 349 nm/min. The deposited films have an adhesionto glass of about 5B. The deposited films have an adhesion to silicon ofabout 0B to about 5B. The deposited films have a grain size of about46-75 nm. The deposited films have an electrical conductivity of about22.8 μΩ·cm (for 200 nm thick films) and about 17.5 μΩ·cm (for 1 μm thickfilms).

Example 29 Molybdenum/Vanadium/Niobium

The sputter target of Example 29 is prepared using the method of Example1 except the tantalum powder is replaced with vanadium powder having aparticle size of about 10-45 μm. Deposited films are then prepared usingthe methods of Examples 2-13, except the sputter target includingmolybdenum, niobium, and vanadium, is employed. The deposited films havean etch rate of about 243 nm/min. The deposited films have an adhesionto glass of about 1B to about 5B. The deposited films have an adhesionto silicon of about 1B to about 5B. The deposited films have a grainsize of about 50-89 nm. The deposited films have an electricalconductivity of about 35.2 μΩ·cm (for 200 nm thick films) and about 33.2μΩ·cm (for 1 μm thick films).

Example 30 Molybdenum/Niobium/Chromium

The sputter target of Example 29 is prepared using the method of Example1 except the titanium powder is replaced with chromium powder having aparticle size of about 10-45 μm. Deposited films are then prepared usingthe methods of Examples 2-13, except the sputter target includingmolybdenum, niobium, and chromium, is employed. The deposited films havean etch rate of about 441 nm/min. The deposited films have an adhesionto glass of about 3B to about 5B. The deposited films have an adhesionto silicon of about 4B to about 5B. The deposited films have a grainsize of about 45-63 nm. The deposited films have an electricalconductivity of about 27.9 μΩ·cm (for 200 nm thick films) and about 21.4μΩ·cm (for 1 μm thick films).

What is claimed is:
 1. A process comprising the steps of: i) placing asputter target having a target surface in a vacuum chamber; ii) placinga substrate having a substrate surface in the vacuum chamber; iii)reducing the pressure in the vacuum chamber to about 100 Torr or less;iv) removing atoms from the surface of the sputter target while thesputter target is in the vacuum chamber at a pressure of about 100 Torror less, wherein the step of removing atoms from the surface of thesputter target employs a magnetic field and/or an electric field; v)depositing atoms on the surface of the substrate so that a molybdenumcontaining layer is formed, wherein the molybdenum containing layerincludes an alloy having about 50 atomic percent or more molybdenum, 0.5to 45 atomic percent of a second metal element selected from the groupconsisting of niobium end vanadium; and 0.5 to 45 atomic percent of athird metal element selected from the group consisting of tantalum,chromium, vanadium, niobium, and titanium, wherein the third metalelement is different from the second metal element.
 2. The process ofclaim 1, wherein the process is a vapor deposition process at a pressureof about 20 mTorr of less.
 3. The process of claim 2, wherein the stepof depositing includes depositing the molybdenum containing layer on asilicon substrate.
 4. The process of claim 3, wherein the molybdenumcontaining layer is interposed between a substrate layer and aconductive layer containing Cu, Al, Ag, Au, or any combination thereof.5. The process of claim 2, wherein the molybdenum containing layer isdeposited over a layer of a first material, and the process includes astep of depositing a layer of a second material over the molybdenumcontaining layer, wherein the process includes a step of annealing thefirst material, the molybdenum containing layer, and the secondmaterial, wherein the molybdenum containing layer prevents migration ofthe atoms of the first material into the second material.
 6. The processof claim 4, wherein the molybdenum containing layer is deposited over alayer of a first material, and the process includes a step of depositinga layer of a second material over the molybdenum containing layer,wherein the process includes a step of annealing the first material, themolybdenum containing layer, and the second material, wherein themolybdenum containing layer prevents migration of the atoms of the firstmaterial into the second material.
 7. The process of claim 6, whereinthe conductive layer includes copper, and the concentration of copper atthe surface of the silicon containing layer is less than 0.1 atomic % asdetermined by Auger spectroscopy after the annealing step.
 8. Theprocess of claim 1, wherein the molybdenum containing layer has athickness of about 200 nm or less.
 9. The process of claim 6, whereinthe conductive layer includes copper, and the concentration of copper atthe surface of the silicon containing layer is less than 0.1 atomic % asdetermined by Auger spectroscopy after the annealing step.
 10. Theprocess of claim 1, wherein the molybdenum containing layer has anaverage grain size of about 20 nm to about 500 nm.
 11. The process ofclaim 1, wherein the third metal element includes tantalum or titanium.12. The process of claim 1, wherein molybdenum containing layer hasgrains that are elongated having a length to width ratio of greater than5:1.
 13. The process of claim 1, wherein the step of depositing themolybdenum containing layer employs an inert gas.
 14. The process ofclaim 1, wherein the process includes a step of etching a layer of thesputter target to remove an oxide layer.
 15. The process of claim 1,wherein the sputter target includes a plurality of phases including: i)about 40% or more by volume of a first phase based on the total volumeof the sputter target, wherein the first phase includes molybdenum at aconcentration of about 50 atomic % or more, based on the total number ofatoms in the first phase; ii) about 1 to about 40% by volume of a secondphase based on the total volume of the sputter target, wherein thesecond phase includes the second metal element at a concentration ofabout 50 atomic % or more, based on the total number of atoms in thesecond phase, and; iii) about 1 to about 40% by volume of a third phasebased on the total volume of the sputter target, wherein the third phaseincludes about 50 atomic % or more of a third metal element based on thetotal number of atoms in the third phase.
 16. The process of claim 15,wherein the second phase is present at a concentration of 5 volume % ormore, based on the total volume of the sputter target, and the thirdphase is present at a concentration of 5 volume % or more, based on thetotal volume of the sputter target.
 17. The process of claim 15, whereinthe concentration of molybdenum in the sputter target is about 70 atomic% or more.
 18. A device prepared according to the method of claim 1,wherein the device includes the substrate layer and the molybdenumcontaining layer.
 19. The device of claim 18, wherein the molybdenumcontaining layer is characterized as having an etch rate greater than100 nm/min when the deposition layer has a thickness of about 200 nm andthe etching is performed using ferricyanide solution at 25° C.
 20. Thedevice of claim 18, wherein the device is selected from the groupconsisting of a computer monitor, an optical disk, a solar cell, amagnetic data storage device, an optical communication device, adecorative coating, a hard coating, a glass coatings including WEBcoatings, a camera, a video recorder, a video game, a cell phone, asmartphone, a touch screen, a global positioning satellite device, avideo scoreboard, a video billboard, and any other display pane.